A TEMPO-conjugated fluorescent probe for monitoring mitochondrial redox reactions

We report a mitochondrial targeted redox probe (MitoRP) that comprises a nitroxide radical (TEMPO) moiety and coumarin 343. Using isolated mitochondria in the presence/absence of substrates and inhibitors of oxidative phosphorylation, we demonstrated that MitoRP is a useful probe to monitor the electron flow associated with complex I.     

Study on hydration of poly(N-vinylcaprolactam) microgels by near-IR and mid-IR spectroscopy

Hydration of poly(N-vinylcaprolactam) microgels was investigated by near-infrared (NIR) and mid-infrared (MIR) spectroscopy. The thermosensitive microgels were prepared by emulsion polymerization, and turbidity, dynamic light scattering, and differential scanning calorimetry measurements were carried out. In MIR spectra, carbonyl bands consist of three components due to double, single, and zero hydrogen-bonding carbonyl groups as verified by density functional theory calculations. The relative intensities changed critically at the volume phase transition temperature upon heating. In NIR spectra, two absorbance peaks around 5,900?cm^?1 were observed, which can be assigned to the first overtone of C–H bands. Both of them undergo red shifts during the phase transition in a similar way to that of fundamental bands in MIR spectra. The result suggests that NIR spectroscopy may be a new general method that can provide new information for research on hydration of thermosensitive microgels.     

Synthesis of unsymmetrically disubstituted ethynes by the palladium/copper(I)-cocatalyzed sila-Sonogashira–Hagihara coupling reactions of alkynylsilanes with aryl iodides,bromides, and chlorides through a direct activation of a carbon–silicon bond

In this paper, we explore the copper/palladium-cocatalyzed cross-coupling reactions of 1-aryl-2-trimethylsilylethynes with aryl iodides, bromides, and chlorides as coupling partners, to furnish unsymmetrically disubstituted ethynes in moderate to excellent yields. Various aryl iodides were subjected to reaction under the optimized conditions with 5 mol % of Pd(PPh₃)₂ and 50 mol % of CuCl. The steric properties of the aryl iodide proved more influential to the outcome of the cross-coupling reaction than electronic factors. In addition, we succeeded in synthesizing unsymmetrical diarylethynes using two different aryl iodides in one-pot. Furthermore, under the same reaction conditions with 10 mol % of PdCl₂, 40 mol % of P(4-FC₆H₄)₃, and 50 mol % of CuCl as catalyst, we succeeded in synthesizing unsymmetrical diarylethynes from various aryl bromides. Finally, we explored reactions with aryl chlorides and duly discovered that unsymmetrical diarylethynes were obtainable in moderate to good yields when 10 mol % of Pd(OAc)₂, 10 mol % of (?)-DIOP, and 10 mol % of CuCl were used. These reactions proceed through a direct activation of a carbon–silicon bond in alkynylsilanes by CuCl to generate the corresponding alkynylcopper species via transmetalation from silicon to copper. Mechanistic investigations on the reaction of alkynylsilanes with aryl bromides confirmed that the trimethylsilyl bromide generated in situ retarded both transmetalation steps between CuCl and alkynylsilane, and between palladium(II) species formed by oxidative addition and alkynylcopper species.     

Generation of radical species from dihydropyrazines having DNA strand-breakage activity and other characteristics

The various biological activity of dihydropyrazines(DHPs)due to the radical generation potency has been described in previous papers. Detailed data about radical species generating be mentioned here. The electron spin resonance (ESR) spin-trapping technique revealed that DHPs generate free radical species such as ·OH, ·OOH, ·CHR(2) and ·CR(3). Oxygen radicals and two carbon-centered radicals were detected as adducts of the spin traps DMPO and DBNBS, respectively. All the 5,5-dimethyl-1-pyrroline-N-oxide (DMPO)- and 3,5-dibromo-4-nitrosobenzenesulfonate (DBNBS)-adducts of compounds DHP-1-8 exhibited approximately the same signal patterns, with various levels of intensity depending on the substituent of the dihydropyrazine ring. The ESR signal intensity of DHPs also increased remarkably upon addition of Cu(2+), resulting that the effects of DHPs were enhanced.     

Theory of the Domino Dynamics Via Nonadiabatic Transitions

Photoinduced nucleation processes, called photoinduced domino processes, via excited electronic states are discussed theoretically for a one-dimensional arrangement of deformable molecules using a model composed of localized electrons and lattices. We show that the global structural transition by photoexcitation only at a molecule (site) is possible in the adiabatic and diabatic limits. An intermediate regime between these limits is investigated; an analytical treatment and a numerical calculation are presented taking into account the nonadiabatic electronic transition, i . e ., the Landau-Zener-type transition. In this regime, the domino dynamics can be terminated halfway ( i . e ., a finite - size domain appears) in contrast to the "all-or-nothing" domino dynamics ( i . e ., a photoinduced domain vanishes or grows up to the system size) in the adiabatic and diabatic limits.     

Effect of substrate temperature on the magnetic properties and internal stresses of CoPt/AlN multilayer deposited by dc magnetron sputtering

Magnetic properties and internal stresses of AlN(20 nm)/[CoPt(2 nm)/AlN(20 nm)]₅ multilayer structure deposited at different substrate temperatures by dc magnetron sputtering have been studied. It is found that with increasing the substrate temperature from room temperature to 400 °C, in-plane magnetic anisotropy field of the film becomes smaller, and the out-of-plane magnetization becomes stronger. Especially when the film is deposited at substrate temperature of 400 °C, the out-of-plane magnetization becomes as strong as the in-plane magnetization. On the other hand, the total in-plane residual stress of the film changes gradually from compressive to tensile. The compressive intrinsic stress is generated during deposition process and decreases with increasing the substrate temperature. After annealing at high temperatures, the films show strong perpendicular magnetic anisotropy. With increasing the annealing temperature, the in-plane thermal stress also increases and becomes dominant, which is considered to result in the perpendicular magnetic anisotropy of the films.     

First observation of o-Ps to p-Ps transition and first direct measurement of positronium hyperfine splitting with sub-THz light

Positronium is an ideal system for the research of the bound state QED. The hyperfine splitting of positronium (Ps-HFS, about 203 GHz) is an important observable but all previous measurements of Ps-HFS had been measured indirectly using Zeeman splitting. There might be the unknown systematic errors on the uniformity of magnetic field. We are trying to measure Ps-HFS directly using sub-THz radiation. We developed an optical system to accumulate high power (about 10 kW) radiation in a Fabry-Pérot resonant cavity and observed the positronium hyperfine transition for the first time.     

Time-domain interferometry experiments using multi-line nuclear absorbers

Langmuir-Blodgett (LB) films of octadecanoyl hydroxamic acid (C18N) complexed with Fe^3?+? ions have been prepared at various subphase pH values. The LB films consisting of different number of layers were investigated by ⁵⁷Fe conversion electron M?ssbauer spectroscopy (CEM) at room temperature. The CEM detector contained a piece of α-iron, enriched with ⁵⁷Fe, using as an internal standard. The M?ssbauer pattern of the C18N/Fe LB films is a doublet with parameters δ = 0.35?mm/s and Δ = 0.74?mm/s. A gradual increase of the relative occurrence of the doublet compared to the sextet of the internal standard was observed with the increasing number of layers, indicating the nearly uniform distribution of Fe among the LB layers.     

A basis for S k (Γ 0(4)) and representations of integers as sums of squares

In this paper, we find a basis for the space S _k (?? ₀(4)) of cusp forms of even weight k for the congruence subgroup ?? ₀(4) in terms of Eisenstein series. As an application, we obtain formulas for r _4s (n), the number of ways to represent a nonnegative integer n as a sum of 4s integral squares.